RU2646216C2 - Hydraulic cleaning supported catalysts with higher activity - Google Patents

Abstract

FIELD: technological processes.

SUBSTANCE: present invention provides for the supported catalysts, the method for its preparation, as well as the method for hydrotreating, hydrodeodization and/or hydrodesulfurization using the supported catalysts. Supported catalyst comprises the carrying agent, phosphorus, at least one Group VIB metal, at least one Group VIII metal and the polymer, where the polymer is present in the catalyst in the amount of about 1.5 WT% or more relative to the total weight of the other components in the catalyst. Molar ratio between the phosphorus and the VIB group metal is from about 1:1.5 up to less than about 1:12. Molar ratio between the Group VIB metal and the Group VIII metal is from about 1:1 up to about 5:1. Polymer has the carbon skeleton (the main chain) and contains the functional groups, which contain at least one heteroatom. Method for preparing the supported catalyst includes the following: I) combining the components together in any of the following combinations: a-i) the carrying agent, one or more monomeric components, the polar solvent and, optionally, the initiator, b-i) the carrying agent, one or more monomeric components, at least one phosphorus compound, at least one Group VIB metal compound and at least one Group VIII metal compound, and optionally the initiating agent, or c-i) the carrying agent and the impregnating solution that form the impregnated carrying agent, followed by mixing the impregnated carrying agent with one or more monomer components and optionally the initiating agent in order to obtain the monomer-containing mixture, where the mentioned monomer component dissolves in the polar solvent and contains the carbon-carbon unsaturated bond and at least one functional group that contains at least one heteroatom; and II) polymerization of at least the portion of the mentioned monomer component in the monomer-containing mixture in order to produce the polymerized product; III) when step I) does not involve the use of at least one phosphorus compound, at least one Group VIB metal compound and at least one Group VIII metal compound, any action from a-iia) contacting the impregnation solution and the monomer-containing mixture during polymerization in step II) or a-iib) contacting the polymerized product and the impregnating solution.

EFFECT: catalysts prepared in accordance with the invention show the high activity during hydrodesulfurization and hydrodezotization; in addition, in the polymer-modified catalysts, the hydrogenating metals are dispersed to a greater extent, than in similar catalysts that did not undergo polymer modification.

22 cl, 2 dwg, 9 tbl, 13 ex

Description

FIELD OF TECHNOLOGY

The present invention relates to supported catalysts obtained from concentrated solutions containing a Group VI metal, a Group VIII metal and phosphorus.

BACKGROUND

A large number of catalysts are known and / or commercially available for hydrotreating, hydrodesulphurisation and / or hydrodeazotization. Many of these catalysts, some of which contain molybdenum, nickel or cobalt and phosphorus, are deposited on substrates and are usually prepared by impregnation of the pore space. Efforts in the art are constantly directed towards the production of various and improved catalysts, in particular those which are characterized by higher activity, for hydrotreating, hydrodesulfurization and / or hydrodetotization.

Hydroprocessing catalysts are usually prepared by impregnating a porous support material with a solution containing active metals, followed by drying or calcination (calcination). Calcined catalysts usually exhibit a strong interaction between the metal and the substrate, which leads to a high dispersion of metals. However, there is a theory that the strong interaction between the metal and the substrate in calcined catalysts leads to lower intrinsic activity of the catalyst. Uncalcined catalysts, as a rule, exhibit a weak interaction between the metal and the substrate and high intrinsic activity. Due to the weak interaction between the metal and the substrate, non-calcined catalysts tend to aggregate metals (weak metal dispersion).

SUMMARY OF THE INVENTION

The present invention provides methods for producing catalysts on substrates from concentrated solutions containing a Group VI metal, a Group VIII metal and phosphorus, as well as catalysts prepared by such methods. The catalysts obtained in accordance with the invention exhibit high activity during hydrodesulphurisation and hydrodeazotization. It is assumed that in the polymer-modified catalysts according to the invention, the hydrogenating metals are dispersed to a greater extent than in similar catalysts that have not undergone a polymer modification.

An embodiment of the present invention is a supported catalyst. The supported catalyst contains a support, phosphorus, at least one Group VI metal, at least one Group VIII metal, and a polymer. In the catalyst, the molar ratio between phosphorus and the metal of group VI is from about 1: 1.5 to less than about 1:12, the molar ratio between the metal of group VI and the metal of group VIII is from about 1: 1 to about 5: 1. The polymer in the catalyst has a carbon skeleton and contains functional groups containing at least one heteroatom.

Other embodiments of the present invention include methods for preparing the above-described catalysts on substrates, as well as methods for hydrotreating, hydrodesulfurization and / or hydro-nitriding using the above-described catalysts on substrates.

These and other embodiments and features of the present invention will become more apparent from the following description, drawings and appended claims.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 illustrates the Raman spectrum, confirming the presence of polymerization in the catalyst obtained in Example 5.

FIG. 2 illustrates the Raman spectrum, confirming the presence of polymerization in some samples obtained in Examples 8 and 9.

DETAILED DESCRIPTION OF THE INVENTION

In the text of this document, the phrases “hydrogenating metal” and “hydrogenating metals” generally refer to a metal or metals of group VI or a metal or metals of group VIII. As used herein, the term “Group VI metal” refers to Group VIB metals. The phrases “used as group VI metal trioxide”, “indicated as group VI metal trioxide”, “in terms of group VI metal trioxide”, “represented as their oxides”, as well as similar definitions for Group VIII metals in relation to their monoxides and phosphorus in relation to its pentoxide (P ₂ O ₅ ), refer to the amount or concentration of a metal of group VI, a metal of group VIII or phosphorus, where the numerical value refers to the corresponding oxide, unless otherwise indicated. For example, nickel carbonate may be used, but the amount of nickel is indicated as a value for nickel oxide.

The impregnating solutions used in the practical implementation of this invention contain a polar solvent, phosphorus, at least one metal of group VI and at least one metal of group VIII, while the molar ratio between phosphorus and metal of group VI is from about 1: 1.5 to less than about 1:12, and the molar ratio between the metal of group VI and the metal of group VIII is from about 1: 1 to about 5: 1.

Group VI metal is molybdenum, tungsten and / or chromium; preferably molybdenum or tungsten, more preferably molybdenum. Group VIII metal is iron, nickel and / or cobalt, preferably nickel and / or cobalt. Preferred metal mixtures comprise a combination of nickel and / or cobalt and molybdenum and / or tungsten. When emphasis is placed on the activity of the catalyst in hydrodesulfurization, the combination of cobalt and molybdenum is preferable and preferred. When emphasis is placed on the activity of the catalyst in hydrodeazotization, a combination of nickel and molybdenum and / or tungsten is preferred and preferred. Another preferred combination of hydrogenating metals is a combination of nickel, cobalt and molybdenum.

The Group VI metal compound may be an oxide, oxoacid or ammonium salt of an oxo or polyoxoanion; these compounds of Group VI metals are formally in the +6 oxidation state if the metal is molybdenum or tungsten. Preferred Group VI metal compounds are oxides and oxo acids. In the practical implementation of the present invention, suitable Group VI metal compounds include chromium (III) oxide, ammonium chromate, ammonium dichromate, molybdenum trioxide, molybdenum acid, ammonium molybdate, ammonium paramolybdate, tungsten trioxide, tungsten acid, ammonium metatungstate hydrate, paratungstate compounds . Preferred Group VI metal compounds include chromium (III) oxide, molybdenum trioxide, molybdenum acid, ammonium paratungstate, tungsten trioxide, and tungsten acid. Mixtures of any two or more Group VI metal compounds may be used.

The Group VIII metal compound is usually an oxide, carbonate, hydroxide or salt. Suitable Group VIII metal compounds include, but are not limited to, iron oxide, iron hydroxide, iron nitrate, iron carbonate, iron hydroxycarbonate, iron acetate, iron citrate, cobalt oxide, cobalt hydroxide, cobalt nitrate, cobalt carbonate, cobalt hydroxycarbonate, cobalt acetate cobalt citrate, nickel oxide, nickel hydroxide, nickel nitrate, nickel carbonate, nickel hydroxycarbonate, nickel acetate and nickel citrate. Preferred Group VIII metal compounds include iron hydroxide, iron carbonate, iron hydroxycarbonate, cobalt hydroxide, cobalt carbonate, cobalt hydroxycarbonate, nickel hydroxide, nickel carbonate and nickel hydroxycarbonate. Mixtures of two or more Group VIII metal compounds may be used.

In the practical implementation of this invention, the phosphorus compound is soluble in a polar solvent and, as a rule, is an acid phosphorus compound, preferably a water-soluble acid phosphorus compound, in particular an oxygenated inorganic phosphorus-containing acid. Examples of suitable phosphorus compounds include metaphosphoric acid, pyrophosphoric acid, phosphoric acid, orthophosphoric acid, triphosphoric acid, tetraphosphoric acid and phosphoric acid precursors such as ammonium acid phosphates. Mixtures of two or more phosphorus compounds may be used. The phosphorus compound may be used in liquid or solid form. In some embodiments, the phosphorus compound is preferably a water soluble compound. A preferred phosphorus compound is orthophosphoric acid (H ₃ PO ₄ ).

In the present invention, the polar solvent may be protic or aprotic and, in general, is a polar organic solvent and / or water. Mixtures of polar solvents may be used, including mixtures containing an aprotic solvent and a protic solvent. Suitable polar solvents include water, methanol, ethanol, n-propanol, isopropyl alcohol, acetonitrile, acetone, tetrahydrofuran, ethylene glycol, dimethylformamide, dimethyl sulfoxide, methylene chloride and the like, and mixtures thereof. Preferably, the polar solvent is a proton solvent; more preferably, the polar solvent is water or an alcohol, such as ethanol or isopropyl alcohol. Water is the preferred polar solvent.

When the monomer and the carrier are combined together and the monomer is polymerized before being contacted with the impregnation solution, only the monomer must be dissolved in the polar solvent used before the polymerization. It is preferable to use the same polar solvent to dissolve the monomer and to obtain an impregnating solution, although different solvents can be used if desired. When the impregnation solution and the carrier are combined together to obtain an impregnated carrier before being contacted with the monomer, the monomer must be dissolved in a polar solvent, which may be the same or different from the polar solvent of the impregnation solution; the use of the same polar solvent to dissolve the monomer and to obtain an impregnating solution is preferred, although different solvents can be used if desired.

The polar solvents that form the impregnating solutions must be capable of dissolving phosphorus compounds, group VI metal compounds and group VIII metal compounds, which are used to prepare the impregnating solutions used for the practical implementation of the present invention.

When the monomer component and at least one phosphorus compound, at least one group VI metal compound, at least one group VIII metal compound are joined together before polymerization, the monomer component must dissolve in a solution containing a polar solvent, at least one phosphorus a compound of a metal of group VI; and at least one compound of a metal of group VIII. In general, this solubility of the monomer component is similar to the solubility of the monomer component in a polar solvent without at least one phosphorus compound, at least one group VI metal compound, and at least one group VIII metal compound in solution. When the impregnation solution is brought into contact with the carrier and the monomer component during polymerization, the same solubility requirements apply; namely, the monomer component present must dissolve in a polar solvent in the presence of at least one phosphorus compound, at least one group VI metal compound and at least one group VIII metal compound.

In the text of this document, the term "monomer" is synonymous with the phrase "monomer component". The monomer component contains a carbon-carbon unsaturated bond as a polymerizable component and at least one functional group containing at least one heteroatom. Theoretically, the heteroatom (s) can form a bond or interact with a metal ion, although the formation of bonds or interactions as a whole is not required. Preferred monomers contain functional groups that contain one or more lone electron pairs. Preferably, the functional group of the monomer component contains nitrogen, oxygen, phosphorus and / or sulfur. Examples of suitable functional groups include hydroxyl groups, carboxyl groups, carbonyl groups, amino groups, amide groups, nitrile groups, amino acid groups, phosphate groups, thiol groups, sulfonic groups and the like. Preferred functional groups include hydroxyl groups and carboxyl-containing groups, in particular carboxylic acid groups, ester groups, amido groups and hydroxyl groups; more preferred are carboxylic acid groups.

Thus, suitable monomeric components include acrylic acid, maleic acid, fumaric acid, crotonic acid, pentenoic acid, methacrylic acid, 2,3-dimethacrylic acid, 3,3-dimethacrylic acid, allyl alcohol, 2-sulfoethyl methacrylate, n-propyl acrylate, hydroxymethyl acrylate, 2-hydroxyethyl acrylate, 2-carboxyethyl acrylate, 3-ethoxy-3-oxopropyl acrylate, methyl carbamylethyl acrylate, 2-hydroxyethyl methacrylate, N-vinyl pyrrolidone, acrylamide, methacrylamide, N-isopropyl acrylamide-N, N-isopropylacrylamide-N, N-isopropylacrylamide-N, N-isopropylacrylamide-N, N-isopropylacrylamide-N, N-isopropylacetamide , N-gidroksimetilakrilamid, N-gidroksietilakrilamid, N-metoksimetilakrilamid, N-etoksimetilakrilamid, vinyl sulfate, vinylsulfonic acid, 2-propene-1-sulfonic acid, vinilfosfat, vinylphosphonic acid, dimetilallilfosfat, dietilallilfosfat and similar compounds. A preferred monomer component includes acrylic acid, maleic acid, 2-carboxyethyl acrylate and N-hydroxyethyl acrylamide, in particular acrylic acid. Mixtures of two or more monomer components may be used.

The amount of monomer used to obtain the catalyst according to this invention is expressed in wt.% Relative to the total weight of other components used to obtain the catalyst, with the exception of the polar solvent. The phrases “other components used to prepare the catalyst” and “other components of the catalyst” used in the text of this document refer to the support and chemicals that provide the catalyst with hydrogenating metals and phosphorus. For example, if the total mass of the other catalyst components (except for the polar solvent) is 100 g, 10 wt.% Of the monomer correspond to 10 g. In the practical implementation of the present invention, the amount of monomer is generally about 1.5 wt.% Or more, preferably corresponds to a range from about 1.5 wt.% to about 35 wt.% relative to the total weight of other components of the catalyst with the exception of the polar solvent, with amounts beyond these ranges are included in the scope of the invention. More preferably, the amount of monomer corresponds to a range of from about 3 wt.% To about 27 wt.%, And even more preferably, to a range of from about 5 wt.% To about 20 wt.% Relative to the total weight of the other catalyst components except for the polar solvent.

In order to prevent premature polymerization of the monomer components, an inhibitor (e.g., a radical scavenger) may be included with the monomer. Suitable inhibitors depend on the particular monomer (s). Appropriate inhibitors present in the mixture prior to initiating the polymerization do not adversely affect at least one phosphorus compound, at least one group VI metal compound and at least one group VIII metal compound. When it is necessary to initiate a polymerization reaction, it is desirable to neutralize or remove the inhibitor (for example, by evaporation or introduction of the initiator).

Although the components used in the preparation of the impregnation solution can be combined in any order, it is recommended and it is preferred that one of the components is suspended or dissolved in a polar solvent before the other components are introduced. Preferably, the Group VIII metal compound is administered first; more preferably, the compound of the metal of group VI was introduced after the connection of the metal of group VIII. The phosphorus compound can be introduced at any time, but preferably it is administered after administration of a group VI compound and a group VIII compound. Upon receipt of the solution, stirring can be used, but it is stopped after the solution becomes homogeneous. Similar requirements apply when a monomer and at least one phosphorus compound, at least one Group VI metal compound and at least one Group VIII metal compound are joined together; it is preferable to combine the hydrogenating metal compounds with a polar solvent, then add the phosphorus compound and then the monomer.

Mixing the components of the impregnating solution can be carried out in an environment, i.e. at room temperature and external pressure. Sometimes, to facilitate the dissolution of components, in particular compounds of group VI and compounds of group VIII, elevated temperatures are necessary. Such elevated temperatures typically range from about 50 ° C to about 95 ° C, preferably from about 60 ° C to about 95 ° C. Temperatures exceeding about 95 ° C and / or elevated pressures (for example, during hydrothermal production) can be used, but they are not necessary. If it is desired to include a monomer in the solution whose polymerization is thermally initiated, the temperature to which the solution is heated is kept below the polymerization initiation temperature or, preferably, the monomer component is added after completion of the heating of the solution.

It is convenient to prepare solutions with concentrations that are suitable for further targeted use of the solution. These solutions, as included in this invention, can be used to prepare a supported catalyst. Suitable concentrations based on Group VI metals (or their total content if more than one Group VI metal is present) typically correspond to a range of about 1.39 mol / L to about 6 mol / L, preferably a range of about 2 , 1 mol / L to about 4.2 mol / L.

Known methods for producing more concentrated impregnating solutions are described, for example, in International publication No. WO 2011/023668.

Impregnating solutions according to the invention, obtained as described above, are solutions containing a metal of group VI, a metal of group VIII and phosphorus in a polar solvent. The concentrations of the metal of group VI, the metal of group VIII and phosphorus, as well as their preferred values, are described above. In these solutions, the molar ratio between phosphorus and the metal of group VI is from about 1: 1.5 to less than about 1:12, preferably from about 1: 2.5 to less than about 1:12, and the molar ratio between the metal of the group VI and a metal of group VIII is from about 1: 1 to about 5: 1.

Without reference to any particular theory, it is believed that a mixture of components is present in the impregnation solutions of this invention. At the moment, not all of these components are properly characterized. In this regard, for an example of the components present in solutions containing molybdenum and phosphorus, see J. Bergwerff, Ph.D. thesis, Utrecht University, The Netherlands, 2007, Chapter 2C.

When a mixture of reagents is used in the preparation of the solutions, as mentioned above, a mixture of components containing different metals will be in the solution. For example, if a molybdenum compound and a tungsten compound are used, the resulting solution will contain molybdenum and tungsten. In another example, if a cobalt compound and a nickel compound are used, the solution will contain cobalt and nickel. If desired, mixtures of reagents, such as compounds of the metals of group VI, can be used to obtain solution compositions, while the metals of group VI of these compounds are different, and the compounds of metals of group VIII, while the metals of group VIII of these compounds are different.

A method for producing a catalyst according to the invention includes I) joining together a carrier, one or more monomer components, a polar solvent, at least one phosphorus compound, at least one group VI metal compound and at least one group VIII metal compound, and optionally initiator in any of the following combinations:

- a carrier, one or more monomer components, a polar solvent and, optionally, an initiator,

a carrier, one or more monomer components, at least one phosphorus compound, at least one group VI metal compound and at least one group VIII metal compound, and optionally an initiator, or

- a carrier and an impregnating solution forming an impregnated carrier, followed by mixing the impregnated carrier with one or more monomeric components and, optionally, an initiator,

to obtain a monomer-containing mixture, wherein said monomer component is dissolved in a polar solvent and contains a carbon-carbon unsaturated bond and at least one functional group containing at least one heteroatom. Stage II) involves the polymerization of the monomer component in a monomer-containing mixture to obtain a polymerized product. Stage III) is carried out when I) does not include the use of at least one phosphorus compound, at least one group VI metal compound and at least one group VIII metal compound, and includes any action from

- bringing into contact the impregnating solution and the monomer-containing mixture during polymerization in II) or

- bringing into contact the polymerized product and the impregnating solution.

Get the catalyst on the substrate. In this method, the molar ratio between phosphorus and the metal of group VI is from about 1: 1.5 to less than about 1:12, and the molar ratio between the metal of group VI and the metal of group VIII is from about 1: 1 to about 5: 1. The impregnating solutions used in the method contain a polar solvent, phosphorus, at least one metal of group VI and at least one metal of group VIII. The next recommended step is to remove excess solvent from the catalyst on the substrate, for example, by drying.

A feature of this invention is that in the method for producing the catalysts according to the invention there is no aggregation of carrier particles. In other words, the carrier particles remain constant in size and shape during the preparation of the catalysts of the invention. For example, carrier particles with an average particle size of about 2 mm become catalyst particles with an average particle size of about 2 mm.

In the method for producing the catalysts according to the invention, all components of the impregnation solution must be dissolved before initiating the impregnation step. When at least one phosphorus compound, at least one Group VI metal compound, and at least one Group VIII metal compound form part of a monomer-containing mixture, the monomer component is preferably added to the mixture after the mixture has been heated. For monomers with thermally initiated polymerization, the temperature during the preparation of the monomer-containing mixture is maintained below the polymerization initiation temperature.

The monomer-containing mixture contains at least one carrier and at least one monomer component. At least one phosphorus compound, at least one Group VI metal compound, and at least one Group VIII metal compound or impregnation solution are optionally added together with the carrier and one or more monomer components in the preparation of the monomer-containing mixture. It is recommended and preferred to include in the monomer-containing mixture at least one phosphorus compound, at least one Group VI metal compound and at least one Group VIII metal compound (sometimes as an impregnation solution). When at least one phosphorus compound, at least one Group VI metal compound and at least one Group VIII metal compound (sometimes as an impregnating solution) are not included in the monomer-containing mixture, the impregnating solution can be mixed with the polymerized product of the monomer-containing solution; alternatively, the impregnation solution may be brought into contact with the monomer-containing mixture during polymerization.

In the methods of the invention, at least one initiator is typically used in the polymerization of the monomer component to form the polymer. Initiators include heating, radiation (e.g., UV), chemicals, and combinations of the above. When the initiator is a chemical, it usually remains in the composition of the catalyst on the substrate and can affect the performance of the catalyst. Therefore, when it is possible to select more than one initiator, it may be useful to conduct studies to determine which combination of initiator (s) and selected monomer (s) provides the best performance. Another requirement is that the selected initiator (s) and monomer (s) should not adversely affect the solubility of phosphorus, Group VI metal compounds, and Group VIII metal in the impregnation solution (e.g., precipitate). For example, it was found that in the polymerization of acrylic acid with persulfate salts as initiators, potassium persulfate was a better initiator than ammonium persulfate for a catalyst containing nickel, molybdenum and phosphorus. The action of a particular initiator may depend on the concentration of hydrogenating metals present in the catalyst, the monomer, and the conditions under which the catalysis is carried out.

Suitable initiators also depend on the reactivity (polymerization) of the selected monomer (s). For example, ammonium persulfate or potassium persulfate, in combination with a temperature increase from room temperature to 80 ° C, are a suitable combination of initiators for the polymerization of acrylic acid. However, for monomers that do not readily polymerize, a different type of initiator or a different combination of initiators may be required.

Used in the text of this document, the term "carrier" is used to denote the substrate for the catalyst, therefore, the term "carrier" can be used interchangeably with the term "substrate". In the text of this document, the term "carrier" refers to a carrier that is in solid form or has a pre-shaped. Such a carrier advantageously retains its solid form when brought into contact with a polar solvent. The term does not refer to salt precursors, such as sodium aluminate, which is almost completely soluble in a polar solvent. In the General case, the carrier is an inorganic oxide, which forms a particulate porous solid phase, and the composition of the carrier may include traditional oxides, for example, alumina, silica, alumina-alumina, alumina dispersed in it silica-alumina alumina coated silica; silica coated alumina; magnesium oxide; zirconia; boron oxide and titanium dioxide; and mixtures of these oxides. Suitable carriers also include transition aluminas, for example eta, theta or gamma alumina. Preferred supports include silica, alumina, silica-alumina, silica-alumina dispersed therein, alumina coated or silica coated alumina, in particular alumina or alumina containing up to about 20 wt.% Silicon oxide, preferably up to about 12 wt.% Silicon oxide. A carrier containing transition alumina, for example, eta-, theta, or gamma-alumina, is particularly preferred, and gamma-alumina is most preferred.

Typically, the carrier is applied in a conventional manner in the form of spheres or, preferably, extrudates. Examples of suitable types of extrudates have been described in the literature; see, for example, US patent No. 4028227. Particularly suitable for use are cylindrical particles (which may be hollow or not), as well as symmetric and asymmetric multilobal particles (2, 3 or 4 petals). The carrier particles are typically calcined at a temperature in the range of about 400 ° to about 850 ° C before being used in the preparation of the catalysts of the invention.

Although the practical implementation of the present invention does not require a specific pore size, the pore volume of the carrier (measured by adsorption of N ₂ ) generally corresponds to a range of from about 0.25 to about 1 ml / g. The specific surface area generally corresponds to a range of from about 50 to about 400 m ² / g, preferably from about 100 to about 300 m ² / g (measured by the BET method). In the General case, the catalyst is characterized by an average pore diameter in the range from about 7 nm to about 20 nm, preferably in the range from about 9 nm to about 20 nm, as determined by adsorption of N ₂ . Preferably, about 60% or more of the total pore volume is within about 2 nm of the average pore diameter. The above numerical values for the distribution of pore size and surface area were determined after calcination of the support at about 500 ° C for one hour.

The carrier particles are typically characterized by an average particle size of from about 0.5 mm to about 5 mm, more preferably from about 1 mm to about 3 mm, and most preferably from about 1 mm to about 2 mm. Since the size and shape of the support do not change during the preparation of the catalyst, the catalyst is generally characterized by an average particle size of from about 0.5 mm to about 5 mm, more preferably from about 1 mm to about 3 mm, and most preferably from about 1 mm to about 2 mm.

The amount of support used to prepare the catalysts of this invention is from about 40 wt.% To about 80 wt.%, Preferably from about 50 wt.% To about 70 wt.%, And most preferably from about 60 wt.% up to about 70 wt.% relative to the total mass of the carrier, hydrogenating metals and phosphorus, while the hydrogenating metals and phosphorus are represented as their oxides, i.e. excluding polar solvent and monomer component.

Methods for impregnating a carrier are known to those skilled in the art. Preferred methods include co-impregnating at least one phosphorus compound, at least one Group VI metal compound, and at least one Group VIII metal compound. In the method for producing the catalysts of this invention, only one impregnation step is required. In a single impregnation step, after the carrier and the impregnation solution are combined together, the mixture is usually homogenized until almost the entire impregnation solution is absorbed by the catalyst. In this method, which is known in the art as impregnation of the pore space or impregnation by moisture capacity, the impregnation solution is almost completely absorbed by the pores of the catalyst, which contributes to the efficient use of chemicals and avoids contamination of the product.

There are a large number of variations of the impregnation method. Thus, it is possible to apply many stages of impregnation, used impregnation solutions containing one or more precursors of the components for application or parts thereof (sequential impregnation). Instead of impregnation methods, dipping methods, spraying methods and so on can be used. When carrying out multiple stages of impregnation, dipping, etc., drying may be carried out between the stages of impregnation. However, a single impregnation step is preferable since it is a faster, simpler process providing higher productivity and is less costly. A single impregnation step also provides higher quality catalysts.

When at least one phosphorus compound, at least one Group VI metal compound, and at least one Group VIII metal compound form part of a monomer-containing mixture, the polymerization of the monomer component is preferably carried out after the impregnation step, although the polymerization can also begin during the impregnation of the support. If the polymerization is carried out after impregnation, the polymerization can be carried out before or during removal of the excess solvent in the event that the excess solvent is removed; preferably, polymerization is carried out while removing excess solvent. Similarly, when the impregnation solution and the carrier are combined together to obtain an impregnated carrier, which is then mixed with the monomer, the polymerization is preferably carried out during removal of the excess solvent in the event that the excess solvent is removed.

In the method according to this invention, the polymerization is carried out in the usual way, exposing the monomer component to the initiator in an amount sufficient to polymerize at least a portion of the monomer. In the presence of any inhibitor, it must be inactivated at the beginning of the polymerization reaction.

When at least one phosphorus compound, at least one Group VI metal compound and at least one Group VIII metal compound do not form part of a monomer-containing mixture, polymerization is initiated in the presence of a carrier before impregnation, and the impregnation solution is added to the monomer-containing mixture during polymerization or after its completion.

Examples of polymers forming part of the catalysts of the invention include, but are not limited to, polyacrylic acid, polymaleic acid, polyfumaric acid, polycrotonic acid, poly (pentenoic) acid, polymethacrylic acid, polydimethacrylic acid, poly (allyl) alcohol, poly (2- sulfoethyl) methacrylate, poly (n-propyl) acrylate, poly (hydroxymethyl) acrylate, poly (2-hydroxyethyl) acrylate, poly (2-carboxyethyl) acrylate, poly (3-ethoxy-3-oxopropyl) acrylate, poly (methylcarbamylethyl) acrylate, poly (2-hydroxyethyl) methacrylate, polyvinylpyrrolidone, polyacrylamide, polymethacrylamide, poly (N-isopropyl) acrylamide, polyvinyl acetamide, polyvinyl-N-methylacetamide, poly (N-hydroxymethyl) acrylamide, poly (N-hydroxyethyl) acrylamide, poly (N-methoxymethyl) acrylamide ethoxymethyl) acrylamide, polyvinyl sulfate, polyvinyl sulfonic acid, poly (2-propyl) -1-sulfonic acid, polyvinyl phosphate, polyvinyl phosphonic acid, poly (dimethylallyl phosphate), poly (diethylallyl phosphate), polyvinyl phosphonic acid. As noted above, mixtures of two or more monomeric components that form copolymers can be used.

Although the monomers used to prepare the supported catalyst are often soluble in polar solvents such as water, the polymer obtained from the monomer (s) need not be soluble in water or other polar solvents.

The methods of the present invention make it possible to obtain catalysts on substrates in which a Group VIII metal is usually present in an amount of from about 1 to about 10 wt.%, Preferably from about 3 to about 8.5 wt.%, Calculated on the monoxide. In these catalysts, phosphorus is usually present in an amount of from about 0.5 to about 10 wt.%, More preferably from about 1 to about 9 wt.%, In terms of P ₂ O ₅ . When the Group VI metal in the catalyst is molybdenum, it is usually present in an amount of about 35 wt.% Or less, preferably in an amount of about 15 to about 35 wt.%, Based on molybdenum trioxide.

When at least one phosphorus compound, at least one Group VI metal compound, and at least one Group VIII metal compound or impregnation solution are introduced before or during polymerization, a catalyst on the support is obtained at the end of the polymerization step. If instead a polymerized product is obtained and then brought into contact with the impregnation solution after polymerization, a catalyst on the support is obtained at the end of the impregnation step or steps.

Excess solvent is optionally removed from the catalyst on the support. Removal of excess solvent can be carried out in air, under vacuum or in the presence of an inert gas. Preferably, solvent removal is achieved by drying the catalyst on a support. The drying of the catalyst on the substrate is carried out under conditions in which at least a portion of the polymer remains in the catalyst, i.e. the polymer is not completely removed upon decomposition. Thus, the drying conditions used depend on the decomposition temperature of the particular polymer; decomposition may include combustion if drying is carried out in the presence of oxygen. In these methods of the invention, drying should be carried out under conditions in which about 50% or more, preferably about 70% or more, more preferably about 90% or more of the polymer remains in the catalyst after drying. Preferably, as much polymer as possible remains on the substrate during drying in the catalyst; however, it is understood that it is not always possible to avoid the loss of a certain amount of polymer during the drying step, at least in the case of more readily degradable polymers. Depending on the polymer, a drying temperature may be necessary lower than about 270 ° C.

As mentioned above, the supported catalyst of this invention contains a carrier, phosphorus, at least one Group VI metal, at least one Group VIII metal and a polymer, wherein the molar ratio between phosphorus and Group VI metal is from about 1: 1, 5 to less than about 1:12, the molar ratio between the metal of group VI and the metal of group VIII is from about 1: 1 to about 5: 1, and the polymer has a carbon skeleton and contains functional groups containing at least one heteroatom. Carriers and preferred requirements are described above. The amount of support in the catalysts on the support according to this invention is from about 40 wt.% To about 80 wt.%, Preferably from about 50 wt.% To about 70 wt.%, And more preferably from about 60 wt.% To about 70 wt.%, Relative to the total mass of the carrier, hydrogenating metals and phosphorus, while the hydrogenating metals and phosphorus are presented in the form of their oxides, i.e. excluding polymer. Hydrogenating metals and their preferred requirements are described above. In polymers, the carbon skeleton is sometimes called the carbon-carbon skeleton, while the skeleton is the main chain of the polymer. Polymers in catalysts on substrates and their preferred requirements are described above.

Optionally, the catalysts of the invention can be subjected to a sulfidation (treatment) step to convert metal components to their sulfides. In the context of the present invention, the definitions of “sulfidation step” and “sulfidation step” include any processing step in which a sulfur-containing compound is added to the catalyst and in which at least a portion of the hydrogenating metal components present in the catalyst are converted to a sulfide form, as directly and after activation treatment with hydrogen. Appropriate sulfidation processes are known in the art. The sulfidation step can take place in an ex situ reactor, in which it is planned to use a catalyst for hydrotreating hydrocarbon feedstocks, in situ, or in a combination of ex situ and in situ reactors.

The ex situ sulfidation process takes place outside the reactor, in which it is planned to use a catalyst for hydrotreating hydrocarbon feedstocks. In such a process, the catalyst is brought into contact with a sulfur compound, for example, an organic or inorganic polysulfide or elemental sulfur, outside the reactor and, if necessary, dried, preferably in an inert atmosphere. In a second step, the material is treated in a reactor with hydrogen gas at an elevated temperature, optionally in the presence of a feed, to activate the catalyst, i.e. to bring the catalyst into a sulfidated state.

The in situ sulfidation process takes place in a reactor in which it is planned to use a catalyst for hydrotreating hydrocarbon feedstocks. In this case, the catalyst in the reactor is brought into contact at an elevated temperature with a stream of hydrogen gas mixed with a sulfidizing agent, such as hydrogen sulfide or a compound which decomposes into hydrogen sulfide (for example, dimethyl disulfide) under these conditions. You can also use a stream of gaseous hydrogen mixed with a hydrocarbon feed containing a sulfur compound, which under these conditions decomposes into hydrogen sulfide. In the latter case, it is possible to sulfide the catalyst by bringing it into contact with a hydrocarbon feed containing an added sulfiding agent, such as dimethyldisulfide (enriched hydrocarbon feed), and it is also possible to use a sulfur-containing hydrocarbon feed without added sulfiding agents, since the sulfur components present in the feed in the presence of a catalyst will be converted to hydrogen sulfide. Combinations of various sulfiding methods may also be used. The use of enriched hydrocarbon feeds may be preferred.

When the catalyst is subjected to an in situ sulphidation step, the catalyst is subjected to high temperatures in the presence of oil and water formed during the process before sulphidation is completed. This exposure to high temperatures in the presence of oil and water does not adversely affect catalytic activity. Without reference to any particular theory, it is believed that the polymer is more resistant to leaching and evaporation compared to catalysts described in the art that contain low molecular weight organic additives.

The compositions of the catalysts according to this invention are those obtained by the above method, regardless of whether this method includes a sulfidation step or not.

Without reference to any particular theory, the observed greater dispersion of hydrogenating metals and a weak (low) interaction between the metal and the substrate are achieved by using the functional group-containing monomers described above to produce polymers in catalysts on substrates. Presumably, such polymers contribute to the dispersion of hydrogenating metals throughout the pore system. Also, without reference to any particular theory, it is believed that the hydrogenating metals interact with a polymer that disperses the hydrogenating metals in the pore space of the substrate. It is also assumed that activation of the catalyst in a sulfidizing atmosphere leads to the replacement of at least some heteroatoms of the functional groups of the polymer with sulfur, which is believed to help minimize or prevent the clustering of hydrogenating metals into clusters or their interaction with the substrate, while, in turn, it is believed that minimizing cluster formation and / or interaction with the substrate contributes to the observed increased catalytic activity. In addition, it is contemplated that the polymer (after sulfidation) can inhibit sintering of hydrogenating metals, contributing to the stability of the catalyst with the support.

The compositions of the catalysts according to this invention can be used in hydrotreating, hydrodetriding and / or hydrodesulfurization of a wide range of hydrocarbon feedstocks. Examples of suitable feedstocks include middle distillates, kerosene, crude oil, vacuum gas oils, heavy gas oils and the like.

The methods according to the invention are methods for hydrotreating, hydrodetotriding and / or hydrodesulfurization of a hydrocarbon feed, which include contacting the hydrocarbon feed and a catalyst according to the invention. Hydrotreating a hydrocarbon feed includes treating the feed with hydrogen in the presence of a catalyst composition according to the invention under hydrotreatment conditions.

You can apply the traditional conditions of the hydrotreating process, such as temperatures in the range from about 250 ° to about 450 ° C, partial hydrogen pressures at the inlet of the reactor in the range from about 5 to about 250 bar (from about 5 × 10 ⁵ Pa to about 2, 5 × 10 ⁷ Pa), space velocities in the range from about 0.1 to about 10 vol./about. h and a ratio of H ₂ / feed in the range of from about 50 to about 2000 Nl / L.

As shown in the Examples, the polymer load achieved was at least 18% by weight relative to the other catalyst components. The amount of polymer present in the supported catalyst (polymer load) is determined similarly to the amount of monomer relative to other catalyst components, as described above. In other words, the amount of polymers in the catalysts according to this invention is expressed in wt.% Relative to the total weight of other components used to obtain the catalyst, with the exception of the polar solvent. For example, if the total weight of the other catalyst components is 100 g, 10 wt.% Of the polymer correspond to 10 g. In the present invention, the polymer load is generally about 1.5 wt.% Or more, preferably corresponds to a range of about 1.5 wt. % to about 35% by weight relative to the total weight of the other components of the catalyst in terms of their oxides and with the exception of the polar solvent, with amounts outside of these ranges are included in the scope of the invention. When the polymer is polyacrylic acid, it is more preferable that the amount of polymer corresponds to a range from about 3 wt.% To about 27 wt.%, And even more preferably to a range from about 5 wt.% To about 20 wt.% Relative to the total weight of the others catalyst components.

The following examples are provided for illustrative purposes and do not limit the scope of this invention.

In several of the Examples below, carbon yield (C-yield) data are provided. The carbon yield is defined as the% of carbon that was introduced into the sample with monomer and remained after drying the material.

In the following Tables 3, 5, 8 and 9, the catalytic activities are given in the form of constant velocity k _{mass, GDS} and k _{mass, GDA} . The constant velocity k _{mass, GDS} for sulfur was calculated using the following formula:

k _{mass, GDS} = JCSS * 1 / (n-1) * (1 / S ^n-1 - 1 / S ₀ ^n-1 ),

where JCSS is the hourly average feed rate (g _oil / g _cat / h); S is the percentage of sulfur in the product (ppm mass. S); S ₀ - the percentage of sulfur in the feed (ppm mass. S); and n is the order of the hydrodesulfurization reaction. For studies at 20 bar (2.0 × 10 ⁶ Pa) and 45 bar (4.5 × 10 ⁶ Pa), a value of n 1.4 was used. For studies at 90 bar (9.0 × 10 ⁶ Pa), a n value of 1.2 was used.

The constant velocity k _{mass, GDA} for nitrogen was calculated using the following formula:

k _{mass, GDA} = JCSS * ln (N ₀ / N),

where JCSS is the hourly average feed rate (g _oil / g _cat / h); N is the percentage of nitrogen in the product (ppm mass. N); and N ₀ is the percentage of nitrogen in the feed (ppm mass. N). JCSS was calculated based on the weight of the catalyst after calcination in air at 600 ° C.

EXAMPLE 1 - comparative

Monomer polymerization without hydrogenating metals

The solution was obtained by dissolving acrylic acid (AK; 1.8 g) in water (40 g). Ammonium persulfate (or peroxodisulfate, PSA; 0.6 g) dissolved in water (2 g) was added to the solution. To initiate the polymerization reaction, the solution was heated to 70 ° C with vigorous stirring. After reaching 70 ° C, viscosity increased markedly and a clear gel formed. The resulting gel was dried overnight at 120 ° C, which resulted in a white-yellow polymer film.

For Examples 2 and 3, an initial impregnation solution was prepared containing 90 g / L of cobalt as CoO, 491 g / L of molybdenum as MoO₃ and 37 g / l phosphorus as P₂O₅by mixing cobalt carbonate (Co (OH)_X(CO₃)_Y), MoO₃, H₃PO_four (water., 85%) and water in appropriate quantities. The mixture was heated at temperatures above 70 ° C until a clear solution was obtained. No monomer was present in this stock solution.

EXAMPLE 2 - comparative

Monomer polymerization in the presence of hydrogenating metals

AK (1.58 g) was dissolved in 15 g of the above stock solution with vigorous stirring. Then, PSA (0.35 g) dissolved in water (0.53 g) was added to the solution. To initiate the polymerization reaction, the solution was heated to 70 ° C with vigorous stirring. After reaching 70 ° C, viscosity increased markedly. After cooling, an elastic mass formed. The elastic mass was dried overnight at 120 ° C, which resulted in a porous brittle precipitate.

EXAMPLE 3

Obtaining a polymer-modified catalyst containing Co and Mo

A group of samples was prepared with different amounts of acrylic acid (AK) in selected portions of the above stock solution. The amount of ammonium persulfate (PSA) in these samples was constant. The amounts of reagents are shown in Table 1; The C1 series is comparative and contains an initiator but does not contain a monomer. A certain amount of the above stock solution was poured into a round bottom flask. Acrylic acid was added and the contents were mixed by shaking. Ammonium persulfate (PSA) was then added and the contents were mixed by shaking.

For moisture impregnation, gamma alumina extrudates with a surface area of 253 m ² / g were added to the solution and the contents were mixed by shaking. A round-bottom flask was placed for 90 min in a rotary evaporator and subjected to smooth rotation at room temperature. Then the temperature of the water bath was raised to 80 ° C to initiate the polymerization reaction (this temperature was reached in 10 minutes), and then the mixture was kept at 80 ° C for 60 minutes; during this phase, the system remained closed to prevent evaporation. Then, the obtained polymer-modified impregnated extrudates were transferred to an evaporator, dried with cold air, and then with hot air until the product temperature reached about 90 ° C.

The carbon content in the obtained catalysts was determined using a general analysis of carbon content, and the carbon yield in grams and its percentage in the carbon content of the monomer are shown in Table 1.

Table 1 Series one 2 3 four C1 Aluminium oxide 50.00 g 50.00 g 50.00 g 50.00 g 50.00 g Original solution 52.95 g 52.95 g 52.95 g 52.95 g 52.95 g AK 1.81 g 3.60 g 5.40 g 7.20 g 0.00 PSA 0.15 g 0.15 g 0.15 g 0.15 g 0.15 g H ₂ O 5.40 g 3.60 g 1.80 g 0 7.20 g Carbon 0.90 g 1.53 g 2.28 g 3.06 g THERE IS NO DATA C-out one hundred% 85% 85% 85% THERE IS NO DATA

EXAMPLE 4

The study of the activity of catalysts containing Co and Mo

The catalysts obtained in Example 3 were crushed; powder fractions from 125 to 350 μm were isolated by sieving. The operational properties of fractions from 125 to 350 μm in hydrodesulfurization and hydrodeazotization were evaluated. The catalysts were sulfidized by bringing them into contact with enriched dimethyl disulfide (2.5 wt.%) Straight-run gas oil (PHGO) during a two-stage process with a temperature maintained at 250 ° C for 8 hours and at 320 ° C for 5 hours and at 20 bar (2.0 × 10 ⁶ Pa) immediately before the study.

The distribution for the boiling points of two types of straight-run gas oil feedstock, feedstock A and feedstock B is shown in Table 2. Feedstock A contained 1.1678 wt.% Sulfur, 94.4 ppm. nitrogen, and its density was 0.8366 g / ml.

table 2 Raw Material A Raw Material B Raw Material C Boiling point 167 ° C 142 ° C 160 ° C 10 wt.% 205 ° C 197 ° C 245 ° C 20 wt.% 217 ° C 212 ° C 262 ° C 30 wt.% 241 ° C 235 ° C 276 ° C 40 wt.% 256 ° C 250 ° C 292 ° C 50 wt.% 269 ° C 265 ° C 306 ° C 60 wt.% 281 ° C 278 ° C 321 ° C 70 wt.% 294 ° C 291 ° C 338 ° C 80 wt.% 307 ° C 307 ° C 358 ° C 90 wt.% 323 ° C 325 ° C 382 ° C Boiling point 347 ° C 347 ° C 426 ° C

Then, the operational properties of the samples were studied in hydrodesulfurization and hydrodeazotization with straight-run gas oil (PHGO) from feedstock A. The samples were examined at 20 bar; the temperature was 345 ° C, the ratio between H ₂ and oil was 300 Nl / l, and the hourly average feed rate (JCSS) corresponded to a range of 1.31 to 1.42 / hour (g _oil / g _cat / h). Table 3 for different catalysts shows the values of the actual mass of the catalyst in different reactors, used JCSS and the content of sulfur and nitrogen in the samples of the liquid product. The sulfur and nitrogen content was estimated by the average value for samples of the liquid product obtained between 1 and 9 days after the introduction of raw materials A. The used GDS order was 1.4.

The generalized results shown in Table 3 show the activity results obtained in a series of tests with the catalysts prepared in accordance with Example 3, compared with catalyst C1. The comparative catalyst contained cobalt, molybdenum and phosphorus in amounts similar to the studied catalysts according to the invention, and the comparative catalyst was prepared in the presence of ammonium persulfate (initiator), but without monomer. As shown in Table 3, the activity of hydrodesulphurisation (GDS) and hydrodesitrogenation (GDA) increased up to about 14% when the amount of polyacrylic acid was increased from 0% to about 8 wt.%

Table 3 Series Polymer load ^* JCSS Research result Activity S N k _{mass, GDS} k _{mass, GDA} wt.% g _oil / g _cat / h ppm ppm n = 1.4 n = 1 one 2,4 1.39 64.6 35.6 0.65 1.35 2 4.1 1.31 48.8 31.3 0.69 1.45 3 6.1 1.42 57.8 34.1 0.70 1.45 four 8.2 1.42 50.1 32.8 0.74 1,50 C1 0 1.39 65.9 36.5 0.65 1.32 ^* Relative to the total weight of other components of the catalyst except for the polar solvent using the observed carbon yield.

EXAMPLE 5

Obtaining a polymer-modified catalyst containing Ni and Mo

An initial impregnation solution containing 100 g / l of nickel as NiO, 599 g / l of molybdenum as MoO ₃ and 42 g / l of phosphorus as P ₂ O ₅ was prepared by mixing nickel carbonate (Ni (OH) _X (CO ₃ ) _Y ), MoO ₃ , H ₃ PO ₄ (aq., 85%) and water in appropriate quantities. The mixture was heated at temperatures above 70 ° C until a clear solution was obtained. No monomer was present in this stock solution.

To prepare catalyst samples containing Ni, Mo, and P with acrylic acid, the procedure of Example 3 was followed using the stock solution described above and an extruded alumina support with a surface area of 205 m ² / g or 271 m ² / g. When ammonium persulfate (PSA) was used as initiator, a yellow precipitate formed. PSA was replaced with potassium persulfate (PSK), adding it in the same amount as PSA. The amounts of reagents are shown in Table 4; series C2 and C3 are comparative and contain an initiator but do not contain a monomer. The carbon content in the obtained catalysts was determined using a general analysis of carbon content, and the carbon yield in grams and its percentage in the carbon content of the monomer are presented in Table 4.

Table 4 Series C2 A B C C3 Aluminium oxide 53.19 g 53.19 g 50.41 g 50.41 g 50.41 g Surface area 271 m ² / g 271 m ² / g 205 m ² / g 205 m ² / g 205 m ² / g Original solution 45.93 g 45.93 g 45.93 g 45.93 g 45.93 g AK 0 g 7.8 g 7.8 g 15.6 g 0 g UCS 0.18 g 0.18 g 0.18 g 0.18 g 0.18 g H ₂ O 15.6 g 7.8 g 8.06 g 0 g 15.86 g Carbon THERE IS NO DATA 3.20 g 3.19 g 6.86 g THERE IS NO DATA C-out THERE IS NO DATA 82% 82% 88% THERE IS NO DATA

The Raman spectra of the catalysts obtained in Examples 3 and 5 clearly indicate the presence of polymerization. Raman measurements were carried out at an excitation wavelength of 532 nm; laser power was adjusted to avoid sample damage. Spectra were recorded for an exposure time of 10 × 30 s. In FIG. 1 illustrates a typical Raman spectrum obtained for catalyst B from Example 5 (Table 4). The spectrum contains an intense band in the region of 2933 cm ^{– 1} , typical of polyacrylic acid. The less intense bands in the region of 3040 cm ^{– 1} and 3110 cm ^{– 1 are} caused, respectively, by vibrations of ν (CH) and ν (CH ₂ ) _asym. acrylic acid monomer. The high peak intensity at 2933 cm ^{– 1} compared with peaks at 3040 cm ^{– 1} and 3110 cm ^{– 1} clearly indicates that acrylic acid polymerization occurred in this catalyst. To confirm the assignment of various peaks, see, for example, C. Murli and Y. Song, Journal of Physical Chemistry B, 2010, 114, 9744-9750.

EXAMPLE 6

The study of the activity of catalysts containing Ni and Mo

For catalysts prepared with acrylic acid, there is an obvious advantage in activity compared to samples not containing monomer (polymer). In this Example, we studied the activity of the catalysts obtained in Example 5 by the method described in Example 4, except that different raw materials were used for the study, and the reactors were operated at 90 bar (9.0 × 10 ⁶ Pa), and not at 20 bar. The studied raw material was raw material B, which consisted of 50% light recycle gas oil (LHG) and 50% straight-run gas oil (PHGO) and contained 1.1317 wt.% Sulfur, 277 ppm. nitrogen, and its density was 0.8750 g / ml; the distribution for the boiling points of raw material B is shown in Table 2. The temperature was 308 ° C for the GDS and 315 ° C for the GDS study; the ratio between H ₂ and oil was 400 Nl / l, and the hourly average feed rate (HSS) corresponded to a range of 1.66–2.04 / h in the HDA study and 1.14–1.22 / h in the HDS study. Table 5 for different catalysts shows the values of the actual mass of the catalyst in different reactors, used JCSS and the content of sulfur and nitrogen in the samples of the liquid product. The sulfur and nitrogen content was estimated by the average value for samples of the liquid product obtained between 1 and 11 days after the introduction of raw materials B for the study of HDA and between 14 and 22 days after the introduction of raw materials B for the study of HDS. GDS data for comparative catalyst C3 was not obtained due to premature shutdown of the reactor. The order of the GDS was 1.3.

The generalized results shown in Table 5 demonstrate the results on the activity of the catalysts obtained in this Example, in comparison with the corresponding comparative catalyst. The activity of hydrodesulfurization (GDS) and the activity of hydrodeasotization (GDA) increased up to about 20%, when the amount of polyacrylic acid in the catalyst was increased from 0% to about 19 wt.%

Table 5 Series Pl. pov. carrier Polymer load ^* JCSS _GDS JCSS _GDA Research result Activity S N k _{mass, GDS} k _{mass, GDA}  wt.% g _oil / g _cat / h g _oil / g _cat / h ppm ppm n = 1.4 n = 1 C2 271 m ² / g 0 1.14 1.97 307 25.6 0.68 4.7 A 271 m ² / g 8.3 1.22 1.98 324 18.3 0.72 5,4 B 205 m ² / g 8.6 1.19 2.04 255 23.0 0.75 5.1 C 205 m ² / g 18.6 1.15 1.95 173 15,5 0.82 5,6 C3 205 m ² / g 0 THERE IS NO DATA 1.66 THERE IS NO DATA 20,4 THERE IS NO DATA 4.3 ^* Relative to the total weight of other components of the catalyst except for the polar solvent using the observed carbon yield.

EXAMPLE 7 - comparative

Polymerization of various monomers in the absence of hydrogenating metals

Several aqueous solutions were prepared, each with an excellent monomer and potassium persulfate (PSK). Monomers, the amount of monomer, UCS and water are shown in Table 6. Pure solutions were obtained by mixing all the components at room temperature. After that, each solution was heated in a closed container at 80 ° C. Visual changes of each solution at elevated temperature made it possible to judge whether polymerization occurred. According to these observations, the polymerization of all monomers studied occurred, with the exception of ethylene glycol vinyl ether.

Table 6 Monomer Number of monomer Amount of water Number of CPM Observations (above 50 ° C) Acrylic acid 7.5 g 22.2 g 0.06 g at 57 ° C clear gel 2-carboxyethyl acrylate 7.5 g 22.7 g 0.06 g at 75 ° C gel; cooling precipitation Maleic acid 7.1 g 24.8 g 0.05 g cooling precipitation N-hydroxyethyl acrylamide 7.5 g 22.7 g 0.06 g at 55 ° C yellow gel Ethylene glycol vinyl ether 7.5 g 21.8 g 0.06 g without changes

EXAMPLE 8

The polymerization of various monomers in the presence of a carrier of Al ₂ O ₃

Several aqueous solutions were prepared, each with an excellent monomer, potassium persulfate and Al ₂ O ₃ extrudates (surface area, BET: 266 g / m ² ), with a concentration of 0.24 g of monomer / g Al ₂ O ₃ and 0.012 g K ₂ S ₂ O ₈ / g Al ₂ O ₃ . The monomers are shown in Table 7. The obtained extrudates, saturated with aqueous solutions of monomers, were heated in a closed container for 16 hours at 80 ° C. Next, the samples were kept at 120 ° C in an open container for 1 hour to remove excess water. The carbon content of the materials thus obtained is shown in Table 7.

For comparison, using the same preparation method, a substrate was prepared loaded with ethylene glycol vinyl ether, which does not polymerize in water (see Example 7). From the data on wt% carbon and C-yield for the comparative C4 series, it is understood that a significant amount of ethylene glycol vinyl ester was released after heat treatment at 120 ° C. This indicates that, in the case of vinyl ether, ethylene glycol did not occur or its polymerization was very incomplete, and that this monomer mostly evaporates during drying at 120 ° C.

Table 7 Carrier Monomer Carbon C-out D Acrylic acid 9.53 wt.% one hundred% E 2-carboxyethyl acrylate 8.17 wt.% one hundred% F Maleic acid 7.08 wt.% one hundred% G N-hydroxyethyl acrylamide 9.77 wt.% one hundred% C4 Ethylene glycol vinyl ether 2.79 wt.% 29%

EXAMPLE 9

Raman measurements for various monomers on Al ₂ O ₃ substrates

For comparison purposes, a carrier sample was prepared. The extruded Al ₂ O ₃ support according to Example 8 was saturated with an aqueous solution of acrylic acid with a concentration of 0.24 g of monomer / g Al ₂ O ₃ in the absence of UCS. Extrudates saturated with an aqueous solution of monomer were heated in a closed container for 16 h at 80 ° C. Further, the extrudates were kept at 120 ° C in an open container for 1 hour to remove excess water. Thus, a comparative sample C5 was obtained.

Raman spectra were recorded for comparative sample C5, as well as for carrier D and carrier F from Example 8 (Table 7); Raman spectra are illustrated in FIG. 2. Raman measurements were carried out at an excitation wavelength of 514 nm; laser power was adjusted to avoid sample damage. Spectra were recorded for an exposure time of 10 × 10 s.

The spectrum of comparative sample C5 contains peaks characteristic of unreacted acrylic acid. The peak at 1640 cm ⁻¹ , which is associated with stretching vibrations C = C, is an obvious sign that unreacted acrylic acid was present in comparative sample C5. The spectrum of carrier D clearly shows the presence of polymerization; the peak at 2929 cm ^{−1 is} characteristic of polyacrylic acid. The absence of a peak at 1640 cm ^{– 1} indicates that C = C bonds were not present in the D carrier. To confirm the assignment of peaks characteristic of acrylic acid and polyacrylic acid, see, for example, C. Murli and Y. Song, Journal of Physical Chemistry B, 2010, 114, 9744-9750. The spectrum of carrier F contains bands that can be attributed to unreacted maleic acid and polymaleic acid. The peak at 2931 cm ⁻¹ indicates the presence of a significant amount of polymaleic acid, while the peaks at 1657 cm ⁻¹ and 3052 cm ⁻¹ indicate the presence of unreacted C = C bonds in the F carrier. To confirm the assignment of peaks characteristic of maleic acid and polymaleic acid, see, for example, CQ Yang and X. Gu, Journal of Applied Polymer Science, 2001, 81, 223-228. Thus, carriers D and F, each of which contained an initiator, contained a significant amount of polymer, while sample C5, which did not contain an initiator, did not contain appreciable amounts of polymer.

These experiments show that the appropriate initiator and / or conditions were necessary for the polymerization of monomers in the presence of carriers. In other words, the carrier itself does not cause polymerization of the monomer (s).

EXAMPLE 10

Obtaining a polymer-modified catalyst containing Co and Mo

The materials obtained in Example 8 were loaded with metal by impregnation of the pore space. A stock solution containing Mo at a concentration of 583 g MoO ₃ / L, Co at a concentration of 104 g CoO / L and H ₃ PO ₄ at a concentration of 42 g P ₂ O ₅ / L was prepared by mixing MoO ₃ , Co (OH) _X ( CO ₃ ) _Y and H ₃ PO ₄ (aq., 85%) and water in appropriate amounts, mixing and heating this mixture at 70 ° C or higher to obtain a clear solution. As an additional comparative sample, using the same initial solution and preparation method, a catalyst was prepared starting with Al ₂ O ₃ extrudates similar to those used in Example 8, but without monomer. For each sample, the initial solution was diluted with sufficient water so that each final catalyst sample contained 28 wt.% MoO ₃ , as measured after calcination at 600 ° C.

EXAMPLE 11

The study of the activity of catalysts containing Co and Mo

The catalysts obtained as described in Example 10 were ground; powder fractions from 125 to 350 μm were isolated by sieving. The operational properties of fractions from 125 to 350 μm in hydrodesulfurization and hydrodeazotization were evaluated. The catalysts were sulfidized by bringing them into contact with enriched dimethyl disulfide (2.5 wt.% S) PG-LGO during a two-stage process with a temperature maintained at 250 ° C for 8 hours and at 320 ° C for 5 hours, immediately before conducting research. The operational properties of the samples in hydrodesulfurization and hydrodeazotization were studied at 45 bar (4.5 × 10 ⁶ Pa) with straight-run gas oil (PHGO) from feed B. Feed B contained 7914 ppm. sulfur, 169 ppm nitrogen, and its density was 0.8574 g / ml; the distribution for the boiling points of raw material B is shown in Table 2. Catalytic activity was determined at a temperature of 350 ° C; the ratio between H ₂ and oil was 300 Nl / l, and the hourly average feed rate (JCSS) corresponded to a range of 2.5-3.5 / hour. Table 8 for different catalysts shows the values of the actual mass of the catalyst in different reactors, used JCSS and the content of sulfur and nitrogen in the samples of the liquid product. The contents of S and N were estimated by the average value for 4 samples of the liquid product obtained between 6 and 8 days after the introduction of raw material B. The used GDS order was 1.4.

Table 8 Series Carrier* Monomer JCSS Research result Activity S N k _{mass, GDS} k _{mass, GDA} g _oil / g _cat / h ppm ppm n = 1.4 n = 1,0 H D Acrylic acid 3.10 31.1 6.5 1.75 10.1 I E 2-carboxyethyl acrylate 2.85 18.1 3.8 2.04 10.8 J F Maleic acid 2.63 15.1 3,1 2.04 10.5 K G N-hydroxyethyl acrylamide 2.71 15.8 3.0 2.06 10.9 C6 C4 Ethylene glycol vinyl ether 2,57 28,4 7.2 1.51 8.1 C7 Al ₂ O ₃ No 2.74 50.6 24.6 1.24 5.3 * See Example 8 and Table 7.

H-K catalysts have an obvious advantage with respect to GDS and GDA activity compared to catalyst C7, to which no monomer was added, and catalyst C6, for which polymerization on the substrate does not occur. The results in the above Table show that the introduction of monomer in the carrier before the introduction of active metals is appropriate, and that the polymerization of the monomer leads to an improvement in catalytic activity.

EXAMPLE 12 - comparative

A commercially available CoMo / Al ₂ O ₃ hydrotreating catalyst containing 24 wt.% Mo as MoO ₃ , 4 wt.% Co as CoO and 2 wt.% P as P ₂ O ₅ was calcined to remove coke and convert sulfides into oxides. The calcination temperature was high enough to remove all coke, but low enough to prevent significant formation of the bulk phase and CoAl ₂ O ₄ . This regenerated CoMo / Al ₂ O ₃ catalyst was sample C8. To obtain sample C9, a certain amount of sample C8 was brought into contact with an aqueous solution of maleic acid. An aqueous solution of maleic acid was used at a concentration of 0.10 g of maleic acid per 1 g of catalyst by impregnation of the pore space. After impregnation, the material was left for 3 hours at 50 ° C in a closed container, after which it was heated to 120 ° C in air to remove water. This maleic acid-contacted catalyst was sample C9. The Raman spectrum of sample C9 did not contain peaks characteristic of polymaleic acid.

EXAMPLE 13 - comparative

The study of the activity of catalysts containing Co and Mo, without polymer

The catalysts described in Example 12 (samples C8 and C9) were ground; powder fractions from 125 to 350 μm were isolated by sieving. The performance properties of fractions from 125 to 350 μm in hydrodesulfurization were evaluated. The catalysts were sulfidized by bringing them into contact with enriched dimethyl disulfide (2.5 wt.% S) PG-LGO during a two-stage process with a temperature maintained at 250 ° C for 8 hours and at 320 ° C for 5 hours, immediately before conducting research. The operational properties of the samples in hydrodesulfurization were studied at 45 bar (4.5 × 10 ⁶ Pa) with straight-run gas oil (PHGO) from feed C. Feed C contained 7914 ppm. sulfur, 169 ppm nitrogen, and its density was 0.8574 g / ml; the distribution for the boiling points of feed C is shown in Table 2. Catalytic activity was determined at a temperature of 350 ° C; the ratio between H ₂ and oil was 300 Nl / l, and the hourly average feed rate (JCSS) corresponded to a range of 2.5-3.5 / h. Table 9 for different catalysts shows the values of the actual mass of the catalyst in different reactors, used JCSS and the sulfur content in the samples of the liquid product. S content was estimated by the average value for 4 samples of the liquid product obtained between 6 and 8 days after administration of PHGO. The used GDS order was 1.4.

Table 9 Series Monomer JCSS Research result Activity S k _{mass, GDS} g of _oil /
g _cat / h ppm n = 1.4 C8 no 3.15 101 1,03 C9 Maleic acid 3.27 107 1,04

A comparison of the results from Table 9 with the results of the J series in Table 8 allows two conclusions. The first conclusion is that the hydrotreating catalyst alone (without a polymerization initiator) does not polymerize the monomer component in the presence of a catalyst. The second conclusion is that in the presence of unpolymerized monomer there is no significant increase in catalyst activity. Thus, in order to guarantee the polymerization of the monomer, appropriate initiator and / or conditions are necessary.

Components denoted by chemical names or formulas anywhere in the text of the description of the invention or claims, regardless of whether they are singular or plural, are defined in the form in which they are in contact with another substance designated chemical name or chemical type (for example, another component, solvent, etc.). It does not matter what chemical changes, transformations and / or reactions, if any, occur in the resulting mixture or solution, if such changes, transformations and / or reactions are a natural result of combining these components together under conditions that are necessary in accordance with this description. Therefore, the components are defined as ingredients for joining together in connection with the necessary actions or upon receipt of the necessary composition. Also, although in the following claims the assignment to substances, components and / or ingredients can be given in the present tense (“contains”, “is”, etc.), the assignment is made to a substance, component or ingredient in the form which they were immediately prior to first contacting, dissolving or mixing with one or more other substances, components and / or ingredients in accordance with the present description. The fact that a substance, component or ingredient could lose its original essence during a chemical reaction or transformation during contacting, dissolving, or mixing operations, if carried out in accordance with this description and by a specialist in the field of chemistry, is not practical fears.

This invention may comprise, consist of, or essentially consist of the materials and / or procedures listed herein.

As used herein, the term “about,” which defines the amount of ingredient in the compositions of the invention or used in the methods of the invention, refers to variations in numerical values that may occur, for example, during typical measurements and operations with liquids used to prepare concentrates, or the use of solutions in real life; due to inevitable errors during these actions; due to the difference in the method of production, source or degree of purification of the ingredients used to obtain the compositions, or the implementation of the methods; and the like. The term about also encompasses amounts that differ due to different equilibrium conditions for formulations obtained from a particular starting mixture. Regardless of the presence or absence of the term "about", the claims include equivalent quantities.

Unless otherwise indicated, the use of the singular in this document does not limit and should not be construed as limiting the description or claims to one element to which this definition refers. More specifically, the use of the singular in this document covers one or more of these elements, unless the text clearly states otherwise.

Each patent or other publication or published document referenced by this invention is included in toto in this description by reference, as if they were fully cited in this document.

This invention admits a variety of variations in its practical implementation. Therefore, the foregoing description is not limiting and should not be construed as limiting the invention to the specific foregoing examples.

Claims (38)

1. The catalyst on the substrate, intended for hydrotreating, hydrodesulfurization and / or hydrodesitration processes, containing a carrier, phosphorus, at least one metal of group VIB, at least one metal of group VIII and a polymer, the molar ratio between phosphorus and the metal of group VIB is from about 1: 1.5 to less than about 1:12, the molar ratio between the metal of group VIB and the metal of group VIII is from about 1: 1 to about 5: 1, and the polymer has a carbon skeleton (main chain) and contains functional groups containing at least one heteroatom, and this polymer is contained in the catalyst in an amount of about 1.5 wt.% or more relative to the total weight of other components in the catalyst. 2. The catalyst according to claim 1, characterized in that the carrier is silica, alumina, silica-alumina, alumina dispersed therein silica-alumina, coated with alumina or coated with silica aluminum, and / or characterized in that the functional groups of the polymer are carboxylic acid groups. 3. The catalyst according to claim 1, characterized in that the molar ratio between phosphorus and the metal of group VIB is from about 1: 2.5 to less than about 1:12. 4. The catalyst according to claim 1, characterized in that the polymer is polymaleic acid, polyfumaric acid or polyacrylic acid. 5. The catalyst according to any one of claims 1 to 4, characterized in that said group VIB metal is molybdenum and / or tungsten, and / or characterized in that said group VIII metal is nickel and / or cobalt. 6. The catalyst according to any one of claims 1 to 4, characterized in that the carrier comprises from about 40 to about 80 wt.% Of the catalyst relative to the total weight of the carrier, hydrogenating metals and phosphorus, while for hydrogenating metals and phosphorus, the calculation is based on them oxides. 7. A method of hydrotreating, hydrodetotriding and / or hydrodesulfurization, comprising contacting a hydrocarbon feed and a catalyst according to any one of claims 1 to 6. 8. A method of producing a catalyst on a substrate, including I) joining together the components in any of the following combinations: a-i) a carrier, one or more monomeric components, a polar solvent and, optionally, an initiator, b-i) a carrier, one or more monomeric components, at least one phosphorus compound, at least one group VIB metal compound and at least one group VIII metal compound, and optionally an initiator, or c-i) a carrier and an impregnating solution forming an impregnated carrier, followed by mixing the impregnated carrier with one or more monomeric components and, optionally, an initiator, to obtain a monomer-containing mixture, wherein said monomer component is dissolved in a polar solvent and contains a carbon-carbon unsaturated bond and at least one functional group containing at least one heteroatom; and Ii) polymerizing at least a portion of said monomer component in a monomer-containing mixture to produce a polymerized product; III) when stage I) does not include the use of at least one phosphorus compound, at least one group VIB metal compound and at least one group VIII metal compound, any of a-iia) contacting the impregnating solution and the monomer-containing mixture during the polymerization in stage II) or a-iib) contacting the polymerized product and the impregnation solution; with the preparation of the catalyst on the substrate, while the molar ratio between phosphorus and the metal of group VIB is from about 1: 1.5 to less than about 1:12, the molar ratio between the metal of group VIB and the metal of group VIII is from about 1: 1 to about 5: 1, said impregnation solution contains a polar solvent, phosphorus, at least one metal of group VIB and at least one metal of group VIII, and the polymer is formed during polymerization, where the polymer in the catalyst contains a carbon skeleton (main chain) and functional groups , soda -containing at least one heteroatom, and wherein the polymer is present in the catalyst in an amount of about 1.5 wt.% or more relative to the total weight of the other components in the catalyst. 9. The method of claim 8, further comprising removing excess solvent from the catalyst on the substrate, so that after said removal of 50% or more of the polymer remains in the catalyst, and / or further comprising sulfiding the catalyst. 10. The method according to claim 8, characterized in that the single step of the impregnation is carried out a) in step I) when the carrier, one or more monomer components, at least one phosphorus compound, at least one metal compound of group VIB and at least one metal compound of group VIII are joined together; b) in step I) by combining the carrier and the impregnation solution together; or c) in stage III). 11. The method according to claim 9, characterized in that the polymerization is carried out while removing excess solvent. 12. The method according to claim 8, characterized in that the carrier, one or more monomer components, at least one phosphorus compound, at least one group VIB metal compound and at least one group VIII metal compound are joined together in stage I) . 13. The method according to claim 8, characterized in that the heteroatom of the functional group of the monomer component is nitrogen, oxygen, phosphorus or sulfur; wherein said support is silica, alumina, silica-alumina, alumina with silica-alumina dispersed therein, alumina coated silica or alumina coated silica; and / or where the molar ratio between phosphorus and a metal of group VIB ranges from about 1: 2.5 to less than about 1:12. 14. The method according to claim 8, characterized in that the functional group of the monomer component is a carboxylic acid group, an ester group or an amido group. 15. The method according to claim 8, characterized in that the monomer component is maleic acid, fumaric acid, acrylic acid, 2-carboxyethyl acrylate or N-hydroxyethyl acrylamide. 16. The method according to p. 12, characterized in that the polar solvent is water; wherein said phosphorus compound is a water soluble acid phosphorus compound; said group VIB metal compound is an oxide or an acid; and / or said Group VIII metal compound is a carbonate, hydroxide or hydroxycarbonate. 17. The method according to clause 16, wherein said group VIB metal compound is a molybdenum compound and / or a tungsten compound, and / or said group VIII metal compound is a nickel and / or cobalt compound. 18. The method according to any one of paragraphs.10-17, characterized in that the carrier is calcined and / or extruded before step I) of this method. 19. The catalyst on the substrate, intended for hydrotreating, hydrodesulfurization and / or hydrodeazotization, obtained by the method according to any one of claims 10-17. 20. The supported catalyst according to claim 19, wherein said group VIB metal is molybdenum and / or tungsten, and / or said group VIII metal is nickel and / or cobalt. 21. The catalyst on the substrate according to any one of paragraphs.19, 20, characterized in that the catalyst is characterized by an average particle size of from about 0.5 to about 5 mm 22. The catalyst on the substrate according to any one of paragraphs.19, 20, characterized in that the carrier is from about 40 to about 80 wt.% From the catalyst relative to the total weight of the carrier, hydrogenating metals and phosphorus, while for hydrogenating metals and phosphorus the calculation is made on their oxides.

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